Dyeing of cellulosic materials



Patented Sept. 2,

rs "r Thomas, Blackley, Manchester, England, assignors to ImperialChemical Industries Limited, a corporation of Great Britain No Drawing.Application April 8, 1935, Serial No.

15,310. In Great Britain April 13, 1934 12 Claims.

This invention relates to dyeing. More particularly it deals with anovel process for dyeing material of vegetable origin, such as textilefiber or non-fibrousmaterial comprising cellulose or cellulosederivatives.

It is an object of this invention 'toprovide a novel process of dyeing,whereby chrome dyestufis, which have hitherto been applicable to animalfibers only, may be made available for dyeing vegetable materials. Otherand further important objects of this invention will appear as thedescription proceeds.

In British Specification No. 398,175 is described a process wherein atextile material composed of cellulose, natural or regenerated, or ofwool or other materials is treated before. or after the dyeing operationwith a dilute aqueous solution of certain heteroc'yclic ammonium salts,but the dyeing processes described relate only to those in which, oncellulosic materials, substantive and directacid dyes are used.

In French Patent No. 725,637, wherein a similar process is described, itis stated that the'improvement is applicable also to acetate silk. Thedyestuffs, however, are again limited to those known as direct and aciddyestufis.

We have. now found that the invention may be extended also to chromedyestufis, such as have heretofore been applicable only to wool andother animal fibers.

More particularly, we have found that material of vegetable origin, suchas cellulosic fiber, both natural and regenerated, or cellulose ethersand esters, may be endowed with an aflinity for chrome dyestuffs, iftreated with a quaternary ammonium salt, of the types mentioned in said1 patents. I v

By chromerdyestufis, we are, referring to such dyestuffs which aregenerally. applied directly 40 from a neutral or acid aqueous solution,and which are fixed upon the fiber by the aid of water-soluble chromatesor bichromates. These latter may be present in the dyeing bath duringthe dyeing operation (the meta-chrome process),

or they may be added to said bath after the dye 5 our invention iscapable of, operation with waterlieu of the soluble organic salts ofinorganic acids, which have the property of ionizing in aqueoussolutionto give a long-chain, organic cation (positively charged ion) and aninorganic anion. In this respect the assistants applicable for our 5novel purpose may be contrasted with ordinary soaps, such as sodiumstearate, palmitate or oleate, which upon ionization give a long-chain,

organic anion and an inorganic cation. By the terms inorganic acids? andinorganic ions in 10 the preceding paragraph as well as in the claimsbelow, we means tocover'and include polybasic inorganic acids or ionswhich have part of their acidity neutralized by organic radicals, as isillustrated by methyl-sulfuric acid which gives rise 15 to themethosulfate ion. According to the invention we treat (mordan so tospeak) cellulose, regenerated cellulosic textile materiaL orcelluloseester or ether material with an aqueous solution of a quaternary 20ammonium, phosphonium or sulphonium salt, the molecule of which containsa saturated'or unsaturated aliphatic chain of at least 10 carbon atomswhich is free of water-solubllizing acid reacting substituents such assulfo or carboxy, and

"mordant processes, orrmodiflcations orcombinations of these methods.

The efiect of our novel process is to endow the fiberwith an afllnityfor the dyestufis in question or for the oxides of chromium or .for

both, and to,produce dyeings of satisfactory fastness towashing and tolight. The fastness tolight of many of the dyeings so produced is of thesame order as that obtained when the dyestuffs are-applied as iscustomary to wool and other animal fibers. Other advantages of. theinvention are indicated below.

Examples of suitable salts for use according to the invention are:octadecyl-pyridinium bromide, the ester of oleic acid andN-hydroxyethylfpyridinium chloride, the cetyl ether of N-.hydrcxy-'methyl-pyridinium chloride, cetyl-trimethyl-am- 5 monium chloride,'dimethyl-dicetyl-ammcnium bromide, cetyl-pyridinium bromide,cetyl-trimethyl-ammonium bromide, octadecyl-trimethylammoniummethyl-sulphate, the trimethyl-ammonium methyl-sulphate ofmonostearyl-ethylene diamine, heptadecylamine hydrochloride, decylaminehydrochloride,dodecylamine hydrochloride cetyl-dimethyl-sulphoniummethyl-sulphate, benzyl-ethyl-dodecyl-sulphonium chloride, andbenzyl-methyl-dodecyl sulphonium methylsulphate. It will be noted thatall the above compounds are free of sulfo or carboxy groups in thecation portion of the molecule, thereby rendering the water-solubilityof the compound more substantially dependent on the character of itsanionic portion.

Some of the above are novel compounds, and are described more fully andclaimed in co-pending applications Serial Nos. 611,236 and 28,013. Theirgeneral schemes of synthesis, however, may be illustrated briefly by thefollowing examples.

Dimethyl-dicetyl-ammonium bromide may be prepared by reacting oneequivalent of dimethylamine and two equivalents of cetyl bromide.Dimethyl-cetyl-sulphonium methyl-sulphate may be prepared by treatingcetyl bromide with sodium hydrosulphide in alcohol, subjecting themercaptan thus formed to an alkylation treatment with dimethyl sulphateand caustic soda, and thereafter obtaining the salt by treatment withdimethyl sulphate alone. Benzylmethyldodecyl sulphonium methyl-sulphateis obtained by treating the mercaptan derived from dodecyl bromide witha mixture of sodium ethoxide and benzyl chloride and finally treatingthe resulting product with dimethyl sulphate.

Further examples of suitable assistants are the sulfonium compoundobtainable by reacting dimetliyl sulphate withZ-octadecyl-mercapto-benzothiazole (in turn obtainable by reacting octadecyl bromide with the sodium salt of 2-mercapto-benzothiazole); andquaternary phosphonium compounds such as cetyl-trimethyl-phos- Dhoniumbromide (obtainable by interacting trimethyl-phosphine and cetylbromide) and dodecyl-trimetlwl-phosphonium bromide (similarly made fromdodecyl bromide and trimethyl-phos- Dhine).

The invention is illustrated but not limited by the follom'ng examples,in which the weight of substances employed in the dye-bath areexpressed, as usual, as percentages of the weight of material to bedyed.

Example I Viscose stockinette is mordanted at 90 C. by immersion forhour in a 40:1 aqueous liquor containing 3.0% ofcetyl-trimethyl-ammonium bromide. It is then thoroughly rinsed, andentered into a warm dye-bath containing 3.0% of the acid chrome dyestuifknown as Solochrome Brown RH (Colour Index No. 98) and 3% of acetic acidand of Glaubers salt. The temperature is gradually raised to 90-95 C.and after hour, 2% of formic acid is added. 'Exhaustion of the dye-bathis satisfactory after a further hour, and 1 /2% of potassium dichromateis added as an aqueous solution. The shade 'is completely developedduring /2-% hour at 95 C. and is of good fastness to lightand Washing(particularly as regards non-staining of adJacent white cotton andviscose).

Example II Viscose stockinette is mordanted by immersion at 9095 C. forV hour in a 40:1 aqueous liquor containing 3%of cetyl-pyridiniumbromide, and is then thoroughly rinsed and entered at 50 C. into adyebath prepared with 3% of the azo acid chrome dyestufi known asSolochrome Brown MG (Colour Index No. 101), 2% of potassium dichromateand 8% of ammonium sulphate and made slightly alkaline with ammonia. Thetemperature is gradually increased to 95 C. and after hour the bath isexhausted satisfactorily without any addition of acid. A full brownshade is obtained of good fastness to washing and light.

Example III Viscose stockinette is mordanted by immersion for hour at 95C. in a 40:1 aqueous liquor containing 3% of cetyl-pyridinium bromideand is then rinsed and entered into a chrome mordanting bath containing3% of potassium dichromate and 2V2% of cream of tartar. The temperatureis maintained at 95 C. for hour, and the material is then rinsed andentered into a warm dye-bath containing 3.0% of the acidchrome dyestufiknown as Solcchrome Orange GR. (Colour Index Supplement, page 52). Thetemperature is gradually raised to 95 C. and after hour, 1% of aceticacid is added. The bath is exhausted satisfactorily and the orange shadeobtained is of good fastness to washing and light.

Example IV Viscose 'stockinette is mordanted with .3% ofcetyl-pyridinium bromide and afterwards with reduced bichrome asdescribed under Example III, and is then rinsed and dyed with 3% of theacid chrome dyestufis known as Solcchrome Red ERS. After dyeing at 90 C.for hour, 1% of acetic acid is added and dyeing continued for a furtherhour when 1% of potassium bichromate is added as an aqueous solution,and dyeing continued for a further minutes.

A full red shade is obtained of good fastness to washing.

Example V Cotton piece goods is mordanted with 3% ofdimethyl-dicetyl-ammonium bromide at 90 C. for hour in a :1 aqueousliquor, and is then rinsed and entered at -60 C. in a dye-bathcontaining 3% of the acid chrome dyestufl. known as Solcchrome Brown MG(Colour Index No. 101), and 2% of acetic acid. The temperature is raisedto 95 C. and after dyeing for hour a further 1% of acetic acid is added.The bath is well exhausted after a further 10 minutes, when 1% ofbichrome is added, and afterchroming performed for hour at 95 C.

The brown shade obtained is of very good fastness to washing.

Example VI Viscose stockinette is mordanted for hour at 90 C. with 3% ofoctadecyl-trimethyl-ammonium methyl-sulphate in a 40:1 aqueous liquor,and is then thoroughly rinsed and entered at C. into a dye-bathcontaining 3% of the azo-acid chrome dyestufi known as Solcchrome BrownMG (Colour Index No. 101) and 2% of acetic acid. The temperature israised to 95 C. and after dyeing has been in progress for hour, afurther 1% of acetic acid is added. Exhaustion is complete during afurther 10 minutes, when 1 of bichrome is added, and afterchroming isperformed at 95 C. for hour when a full brown shade of very goodfastness to washing and light is obtained.

Example VII Viscose stockinette is mordanted with 3.0% ofdimethyl-cetyl-sulphonium methyl-sulphate by immersion for V hour at90-95 C. in the aqueous solution. It is then dyed a red shade byimmersion in an aqueous liquor containing 3% of Solochrome Red 6B (I. C.L Dyestufis Sales Circular S, C. 110), 3.0% of acetic acid and 10% ofGlaubers salt, calculated on the weight of material. After hours dyeingat 9095 C., an addition of 1% of formic acid is made, and after afurther hour a further addition of 1%. Afterchroming is then performedby addition of 1% of potassium dichromate and heating at 9095 C. for.hour. v

The shade obtained possesses very good fastness to washing and light. 7

Example VIII A yellow shade of good fastness properties is obtained.

Example IX Acetate artificial silk stockinette fabric is mordanted forhalf an hour at 75 C. in an aqueous solution-of 3% ofoctadecyi-trimethyl-ammonium methyl-sulphate, the amount of liquor being40 times that of the material. The fabric is well rinsed in warm waterand then put into a dyebath (at 50 C.) containing 3.0% of .the chromedyestuif known as Solochrome Brown M (Colour Index No. 101), and 2% ofacetic acid. The

temperature is increased to C. and after half an hour a further 1% ofacetic acid is added, followed by 1 of sodium bichromate after a further10 minutes.

After chroming for half an hour at SO- C.

- a medium brown shade of good fastness to washing and light isobtained. The dye liquor is exhausted very satisfactorily.

Erample X Acetate artificial silk stockinette fabric is mordanted forhalf an hour at IO-75 C. in an aqueous solution containing 3%.ofcetyl-pyridinium bromide, and is then dyed with 2% of the chromedyestuif known as Solochrome Yellow'C (Colour Index No. 343), by theafterchrome process as described in Example IX. The dye liquor is wellexhausted, and a good yellow shade is obtained.

Example XI Acetate artificial silk stockinette is mordanted with 3% ofcetyl-pyridinium bromide as in Exwith 3.0% of the chrome dyestuif knownas Solochrome Yellow WN (Colour Index No. 36). 2% of sodium bichromateand 4% of ammonium sulphate is employed in the dye-bath, and dyeing isperformed at 80 C. for three quarters of an hour. A good yellow shade isobtained.

Example XII Acetate artificial silk stockinette fabric is mordanted with3% of dimethyl-dicetyl-ammonium bromide .at IO-75 C. for half an hour,from an aqueous solution of the quaternary ammonium compound. Themordanted material is well rinsed in water and then heated for threequarters of an hour at ZS-80 C. in an aqueous solution containing 3% ofpotassium bichromate and 3% of cream of tartar. The chrome mordantedmaterial is then rinsed and entered at 50 C. into a dye-bath containing4% of the chrome dyestufl known as Solochrome Brown NH (Colour Index No.105). The temperature is increased to 80 C. and after half an hour 1% ofsulphuric acid and 1% of potassium bichromate (as concentrated aqueoussolution) are added in order to developthe shade fully.

A medium brown shade is obtained.

Example XIII Glycol-cellulose is mordanted by treatment for half an hourat -95 C. in an aqueous solution of cetyl-pyridinium bromide containing3% of the quarter-nary ammonium compound on the weight ofglycol-cellulose. The material is then rinsed and dyed by theafterchrome process at 90-95 C. with 3% of the chrome dyestuif known asSolochrome Cyanine R (Colour Index No. 722), with the addition of 3% ofacetic acid to the dyebath and 2% of formic acid for exhaustion.Afterchroming is performed with the addition of 1 of sodium bichromatewhen a full bright blue shade is obtained of excellent fastness towashing. I

Example XIV Ethylcellulose powder is mordanted at 90 C. from an aqueoussolutioncontaining 3% of cetylpyridinium bromide, by treatment for halfan hour. It is then filtered off, washed with water and dyed by theafter-chrome process with 3% of the chrome dyestuif known as SolochromeAzurine B (Colour Index 'No. 720). The temperature is maintained at90-95 C. during the dyeing and chroming operations. 3% of acetic acidand1% of formic acid are employed in the dye-bath. The dark blue powderobtained may be dissolved in acetone or ethyl alcohol to give a deepblue solution of high tinctorial value from which blue films can beobtained.

Example XV Ethyl cellulose powder mordanted as described in Example XIVis dyed by the afterch'rome process at 90-95 C. with 3% of the chromedyestuif known as Solochrome Yellow C (Colour Index 343). dark yellowpowder is 'obtained"which may be dissolved in acetone or alcohol to givea deep yellow solution which yields a yellow film.

Example XVI Acetate artificial silk stockinette is mordanted at 75 C.for half an hour from an aqueous solution containing 3% ofdimethyl-cetyl-sulphoni'um" dyed by the afterchrome process at 75-80 C.with ample X, and is dyed by the metachrome process 3% of the chromedyestuff known as Solochrome Yellow .C (Colour Index No. 343), 3% ofacetic acid, and 1% of sulphuric acid are employed in the dye-bath, and1 of potassium bichromateis employed for afterchroming. -A yellow shadeof medium depth and good fastness'to washing is obtained.

Example XVII Example X VII 1 Viscose stockinette is mordanted byimmersion at 95 C. for hour in a 40: 1 aqueous liquor containing 3%heptadecylamine hydrochloride. It is then rinsed and dyed by immersionin a dyeliquor set with 3% of the acid-chrome dyestuff known asGallo-cyanine BD (Colour Index 883) and 3% of acetic acid with 10% ofGlaubers salt. The temperature is gradually raised to C. C. After hourat this temperature 2% of sulphuric acid is added and a further /1; hourat 90 C.-95 C. is then suflicient to ensure complete exhaustion. At thisstage 2% of potassium dichromate is added and the shade fully developedin hour to hour. The resultant shade is a strong navy blue of excellentfastness to light and washing.

Example XIX Viscose stockinette is' mordanted by inmiersion for hour at90-95 C. in a 40:1 aqueous liquor containing 3% of heptadecylaminehydrochlor ide. It is then thoroughly rinsed and immersed in a warmdye-bath containing 3% of the acid chrome dyestuff known as SolochromeBrown MG (Colour Index No. 101) and 3% acetic acid with 10% Glauberssalt. The temperature is slowly raised to 90 C.-95 C. After hour at thistemperature a further addition of 2% of sulphuric acid is made to thedye-bath to ensure complete exhaustion which is obtained after a further4 hour. 2% of potassium dichromate is then added and the shade fullydeveloped after /2% hour at 90-95" C. The bright brown shade obtained isof excellent fastness to light and washing.

Example XX Acetate silk stockinette is mordanted by immersion at 75 C.in a 40:1 aqueous liquor containing 3% of heptadecylamine hydrochloridefor hour. It is then rinsed and immersed in a warm dye-bath set with 3%of the acid chrome dyestufi known as Solochrome Brown MG (Colour IndexNo. 101) with 3% 10% Glaubers salt. The temperature is slowly raised to75 C. and after hour at 75 C. 2% of sulphuric acid is added to completethe exhaustion of the dyebath, which is satisfactory after a further 5hour. At this stage 2% potassium dichromate is added and after a furtherhour the shade is fully developed. A bright brown shade is obtainedwhich is of good fastness to light and washing. 1

In place of heptadecylamine hydrochloride there can used other longchain amines such as decylamine hydrochloride or dodecylaminehydrochloride.

' It will be understood that the details pf procedure may be variedwithin wide limits without departing from the spirit .of this invention.

acetic and Thus, while we have indicated in each of the above examples a3% solution of the mordanting organic salt and used it in a ratio of40:1 compared to the weight of the cellulosic material,

thesefigures have been adhered to merely as a standard for comparison.Various other ratios may obviously be employed, and the concentrationmayvary within wide. limits, say from 5% to 10% depending on the intensityof eiiect desired.

Similarly, although in the above examples we worked at temperatures from70 to 95 C., any other convenient temperature between room temperatureand boiling water may be employed. As in the case of mordanting withmetallic oxides, the application of the mordant to the fiber may beeffected by padding, spraying, impregnating or immersion.

Many other variations and modifications will be obvious to those skilledin the art.

We claim: 7

1. A process for coloring textile fiber of cellulosic origin withacid-chrome dyestufi s normally applicable to wool only, which compriseswarming said fiber in an aqueous bath of an organic salt selectedfrom-the group consisting of longchain ammonium, phosphonium, andsulfonium salts of strong mineral acids, the long-chain comprisinganaliphatic chain of at least 10 carbon atoms, and then dyeing said fiberwith an acid- I chrome dyestuff by one of the methods generallyapplicable with dyestuifs of this class.

2. A process for colouring textile material of cellulosic origin, whichcomprises mordanting the same with an aqueous solution of a watersolubleorganic salt selected from the group consisting of organic quaternaryammonium, quaternary phosphonium and ternary sulfonium compounds whichcontain at least one aliphatic chair of not less than 10'carbon atoms,and then dyeing said material withan acid-chrome dyestulf for wool inthe same manner as wool would normally be dyed with a dyestuil. of thesame class.

3. The process whichcomprises mordanting textile fiber comprisingcellulose with an aqueous solution of an organic salt selected from thegroup consisting of quaternary ammonium, quaternary phosphonium andternary sulfonlum derivatives of strong mineral acids, the saltcontaining at least one aliphatic chain, of not less than 10 carbonatoms and which is free of watersolubilizing acid reacting substituents,and then dyeing said fiber with an acid-chrome dyestuff, by one of theprocesses known as the chromemordant, metachrome, and afterchromemethods.

organic ammonium compound capable of dissociating and yielding apositively charged organic ion comprising a long-chain aliphatic rad- Iical of not less than 10 carbon atoms and being free ofwater-solubilizing acid reacting substi- Qtuents, and then treating thefiber in optional ill time relation with an aqueous solution or anacidchrome dye and an aqueous solution of a chroming agent.

6. A process for colouring textile material of cellulosic origin, whichcomprises mordanting the same with an aqueous solution of an organicam-- monium salt selected from the group consisting of organic ammoniumhalides and organic ammonium methyl-sulfates, the organic radical ofwhich contains at least one straight chain aliphatic radical of not lessthan 10 carbon atoms, and then dyeing said material with an acidchromedyestufi for wool in the same manner as wool would normally be dyed witha dyestufi'of the same class.

."I. A process for colouring textile material of cellulosic origin,which comprises mordanting the same with an aqueous solution of anorganic quaternary ammonium halide which contains in the nitrogen atomat least one straight chain aliphatic radical of from 10 to 18 carbonatoms, said aliphatic radical being free of Water-soluvbilizing'acidreacting substituents, and then dyeing said material with an acid-chromedyestufi, by one of the processes known as the chromemordant,metachrome, and aiterchrome methods.

8. A process for colouring textile material of cellulosic origin, whichcomprises mordanting the same with an aqueous solution of a primaryalkyl ammonium halide the alkyl portion of which contains a straightchain aliphatic radical of from 10 to 18 carbon atoms but nowater-solubilizing acid reacting substituents, and then dyeing saidmaterial with an acid-chrome dyestufl', by one of the processes known asthe chrome-mordant, metachrome, and afterchrome methods.

9. A process for colouring textile material of cellulosic origin, whichcomprises mordanting the same with an aqueous solution of an alkylpyridinium halide the alkyl portion of which contains a straight chain"aliphatic radical of from to 18 carbon atoms, and then dyeing saidmaterial with an acid-chrome dyestuff, by one of the processes known asthe chrome-mordant, metachrome, and afterchrom'e methods.

10. A process for colouring textile material of cellulosic origin, whichcomprises mordanting the same with an aqueous solution ofoctadecyl-trimethyl-ammonium methyl-sulfate, and then dyeingsaidmaterial with an acid-chrome dye-= stufi, by one oi. the processesknown as the chrome-mordant, metachrome, and afterchrome methods. w

11. A process for colouring textile material of cellulosic origin, whichcomprises mordanting the same with an aqueous solution ofcetyl-trimethylammonium bromide, and then dyeing said material with anacid-chrome dyestuif, by one of the processes known as thechrome-mordant, metachrome, and afterchrome methods.

- 12. A process for colouring textile material of cellulosic origin,which comprises mordanting the same with an aqueous solution of cetylpyridinium bromide, and then dyeing said material with an acid-chromedyestuif, by one of the processes knownas the chrome-mordant,metachrome, and afterchrome methods,

LESLIE PAIGE RENDELL.

HARRY AUGUSTUS THOMAS.

